New halogen-containing glycidyl ethers



United States Patent 3,151,129 NEW HALQGEN-CONTAENXNG GLYCIDYL ETHERSErnst Leumann and Hans Eatzer, Arlesheim, Switzerland,

assignors to Ciba Limited, Basel, Switzerland, a company of SwitzerlandNo Drawing. Filed Sept. 12, 1961, Ser. No. 137,322

Claims priority, application Switzeriand dept. 15, 196i? (Iiaims. (Cl.Zeta-348) The present invention provides new halogenated glycidyl ethersof the general formula where n is a small whole number and A representsa cycloaliphatic radical with n free valencies which contains at leastone grouping of the formula where the two radicals Hal represent vicinalhalogen atoms, more especially chlorine or bromine atoms, and R and Reach represents a hydrogen or halogen atom or a lower alkyl radical.

The new glycidyl ethers can be prepared by adding halogen on to thedouble or triple bond respectively in glycerol monohalohydrin ethers orglycidyl ethers of cycloaliphatic monoalcohols or polyalcoholscontaining at least one grouping of the formula J= or -OEC where R and Rhave the above meanings, and, as the case may be, the halohydrin groupor groups is/are then dehydrohalogenated.

Alternatively, the new glycidyl ethers are also obtained by reacting acycloaliphatic monoalcohol or polyalcohol that contains at least onegrouping of the formula i r |l2 Hal Hal where R and R have the abovemeanings, with an epihalohydrin or a glycerol monohalohydrin and theintermediately formed halohydrin group or groups is/ aredehydrohalogenated.

Suitable unsaturated cycloaliphatic monoalcohols or polyalcohols, fromwhich the monohalohydrin ethers or glycidyl ethers respectively arederived, are, for example: Cyclohexene-3 ol 1, A tetrahydrobenzylalcohol, 6- rnethyl-M-tetrahydnobenzyl alcohol, 2:5-endomethylene-M-tetrahydrobenzyl alcohol, dihydrodicyclopentadienol- 8,M-cyclohexene-l:l-dimethanol, 6-methyl-A -cyclohex- .ene-l: l-dimethanoland 2 5-endomethylene-A -cyclohexene-l l-dimethanol.

Preferred starting materials are glycerol monochlorohydrin ethers whichare first halogenated and then dehydrohalogenated to the correspondingglycidyl ethers. In this connection it is extremely surprising that thehalo genation proceeds smoothly and without any noticeable sidereactions; this could not have been expected since it is known that ingeneral the halogenation of unsaturated glycols' gives poor tounsatisfactory yields. For example, the chlorination of butyne-Z-diol-l:4 gives a yield of only 35 of 2:223:3-tetrachlorobutanediol-l:4- inaddition to a substantial proportion of resinification products.

When, instead of the monohalohydrin ether, the glycidyl ether isdirectly halogenated, the resulting yields of 3,151,129 Patented Sept.29, 19641:

performed by reacting the halogen, more especially C1 or B17 upon theunsaturated etherin a suitable solvent such as carbon tetrachloride orbenzene, for example at a temperature ranging from .0 to 25 C.,advantageously from 5 to 15 C. The amount of halogen introduced or usedfrom the start should be suflicient to ensure that the double or triplebond of the unsaturated ether is quantitatively saturated.

The optionally performed subsequent elimination of hydrogen halide inthe case of the halohydrins or chlorohydrins is carried out in knownmanner with solid alkalies or aqueous alkali solutions.

Among the new glycidyethers of the invention those of the generalformula where the two radicals Hal represent chlorine or bromine atoms,R represents a hydrogen atom or a methyl group, and n=1 or 2, areparticularly easy to manufacture.

The halogenated glycidyl ethers of the inventionin contradistinction tothe hitherto known chlorine-containing epoxy resinare only slightlytinted, and, more especially, the derivatives ofAicyclohexene-l:l-dimethanol are, surprisingly almost completelycolorless. Fur-ther more, some of them are of very low viscosity. Thenew diglycidyl and polyglycidyl ethers react with the conventionalcuring agents for epoxy resins so that they can be cured cold or withheating by the addition of such curing agents in the same manner asother polyfunctional epoxy compounds. As such curing agents there may beused either basic or acidic compounds. Particularly good results havebeen achieved with: Amines and amides, such as aliphatic and aromaticprimary, secondary and tertiary amines, for example men diandtri-butyl-amines, paraphenylenediamine, 4:4 diaminodiphenylmethane,ethyl enediamine, N hydroxyethyl ethylenediamine, NzN- diethylethylenediamine, diethylenetriamine, metaxylylenediamine,triethylenetetramine, .trimethylamine, diethylamine, triethanolamine,Mannichs bases, piperidine} piperazine, guanidine and guanidinederivatives, such as phenyldiguanidine, diphenylguanidine,dicyandiamide, formaldehyde resins of urea, melamine or aniline;polymers of aminostyrenes; polyamides, for example those of dimerized ortrimerized unsaturated fatty acids and alkylene-polyamines; isocyanates,isothiocyanates, phosphoric acid, polybasic carboxylic acids and theiranhydrides, for example phthalio anhydride, methyl-endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride,hexahydrophthalic anhyd-ride, hexazinc chloride, boron trifluoride andcomplexes thereof with organic compounds; metal fiuobor'ates, forexample nickel fiuoborate; boroxines such as trimethoxy-boroxine. Themonoglycidyl ethers of the invention by themselves likewise react withthe afore-mentioned curing agents, but in most cases linear reactionproducts are obtained that are not cross-linked. They can becross-linked or cured, for example, with polybasic carboxylic acids andanhydrides thereof. The term curing as used in this connection signifiesthe conversion of the glycidyl ethers into insoluble and infusibleresins.

The curable glycidyl ethers', or their mixtures with curing agents, canbe admixed at any stage prior to the curing with other flame-proofingagents such, for example, as phosphates, or with fillers, softeningagents, coloring matter and similar products. Suitable extenders andfillers are, for example, asphalt, bitumen, glass fibers, mica, quartzmeal, cellulose, kaolin, finely dispersed silicic acid (Aerosil) ormetal powders.

The mixtures of the new glycidyl ethers and the curing agents can beused without or with fillers, in solution or emulsion, as textileassistants, laminating resins, lacquers, varnishes, paints, dipping orcasting resins, coating compositions, pore fillers and putties,adhesives or the like, or for the manufacture of such products.

The new glycidyl ethers can also be used as intermediates and asflame-proofing active diluents or modifying agents for the known epoxyresins, such for example, as are obtained by reacting epichlorohydrinupon a polyhydric phenol, such as resorcinol orbis-[4-hydroxyphenyl1-dimethylmethane, in an alkaline medium.

In the following examples parts and percentages are by weight, and therelationship between part by weight and part by volume is the same asthat between the kilogram and the liter. The epoxide contents shown asepoxide equivalents per kg. have been determined by the method describedby A. J. Durbetaki in Analytical Chemistry, volume 28, No. 12, December1956, pages 2000-2001, with hydrogen bromide in glacial acetic acid.

Example 1 A reaction vessel equipped with stirrer, thermometer, gasinlet tube and cooling bath is charged with a suspension of 327 parts (1mol) of N-cyclohexene-hl-dimethanol-bis(a-monochlorohydrin)ether in 200parts by volume of carbon tetrachloride. While stirring the suspensionwell there are introduced at to C. within 1 hour 71 parts (1 mol) ofchlorine. While continuing to cool the mixture well, it is treateddropwise with 240 parts (3 mols) of sodium hydroxide solution of 50% ata rate such that the temperature does not exceed 0. Initially, thereaction is strongly exothermic, but towards the end it is no longernecessary to cool. To complete the elimination of hydrogen chloride themixture is stirred on for 30 minutes at C., then cooled, the sodiumchloride formed is dissolved by adding 300 parts by volume of water, andthe organic phase is separated, dried over calcium chloride andevaporated under vacuum, to yield 298 parts of an almost colorless,medium viscous liquid which contains, per kg, 4.05 epoxide equivalentsand 6.98 equivalents of chlorine. The product consists predominantly ofthe dichlorinated diglycidyl ether of the formula When this compound iscured for 24 hours at 140 C. with 0.85 mol of phthalic anhydride perequivalent of epoxide groups, With addition of 13.5% oftrixylenylphosphate, the castings so obtained display a VDE flammabilityvalue of 39 seconds.

Example 2 In the reaction vessel used in Example 1 (the gas inlet tubebeing replaced by a dropping funnel) 327 parts (1 mol) ofM-cyclohexene-l:l-dimethanol-bis(a-monochlorohydrin)ether are suspendedin parts by volume of carbon tetrachloride. A solution of 160 parts (1mol) of bromine in 200 parts by volume of carbon tetrachloride is thenadded dropwise from the dropping funnel at a temperature of 10 to 15 C.within 1 /2 hours. As described in Example 1, 240 parts (3 mols) ofsodium hydroxide solution of 50% strength are then dropped in and themixture is stirred for 30 minutes at 50 C. and then cooled; theprecipitated sodium chloride is dissolved by adding 300 parts by volumeof water, and the organic phase is separated and worked up as describedin Example 1, to yield 401 parts of a medium viscous, almost colorlessliquid which contains, per kg, 4.1 epoxide equivalents and 6.25equivalents of bromine. The product consists predominantly of thedibrominated diglycidyl ether of the formula When this product is curedfor 24 hours at room temperature with 0.2 mol of diethylenetriamine perequivalent of epoxide groups, with addition of 13.5% oftrixylenylphosphate, the resulting castings display a VDE flammabilityvalue of 0.5 second.

When the compound is cured with 0.85 mol of phthalic anhydride perequivalent epoxide groups, with addition of 13.5% oftrixylenylphosphate, for 24 hours at C., castings are obtained thatdisplay a VDE flammability value of 0 seconds.

Example 3 254 parts (1 mol) of M-cyclohexene-l:l-dimethanoldiglycidylether are dissolved in 300 cc. of benzene in the apparatus used inExample 1. In the course of 75 minutes 71 parts (1 mol) of chlorine areintroduced at 8 to 10 C., and the solvent is then evaporated undervacuum, to yield 320 parts of a medium viscous liquid containing, perkg., 3.22 epoxide equivalents and 7.88 equivalents of chlorine; itconsists predominantly of the dichlorinated diglycidyl ether describedin Example 1.

Example 4 A solution of 254 parts (1 mol) of A -cyclohexene-1:1dimethanol-diglycidyl ether in 100 parts by volume of benzene is treateddropwise, within 1 hour at 5 to 10 C. with a solution of parts (1 mol)of bromine in 200 parts by volume of benzene. The solvent is thenevaporated under vacuum, to yield 397 parts of a liquid containing. perkg, 3.40 epoxide equivalents and 6.32 equivalents of bromine; itconsists predominantly of the dibrominated diglycidyl ether described inExample 2.

Example 5 As described in Example 2, a solution of 204.5 parts (1 mol)of A -tetrahydrobenzyl alcohol-u-monochlorohydrin ether in 100 parts byvolume of benzene is treated dropwise Within 1 hour at 5 to 10 C. with asolution of 160 parts (1 mol) of bromine in 200 parts by volume ofbenzene.

The subsequent elimination of hydrogen chloride is carried out in twostages: First, parts (1.5 mols) of sodium hydroxide solution of 36.4%strength are dropped into the reaction mixture and the temperature isallowed to rise to about 50 C.; the mixture is stirred for 30 minuteswithout cooling or heating, then cooled and treated with 100 parts byvolume of water; the organic phase is separated and stirred for 40minutes at 50 C. with 80 parts (1 mol) of sodium hydroxide solution of50% strength, again cooled, 100 parts by volume of water are then added,and the organic phase is separated, dried over calcium chloride andevaporated under vacuum.

kg., 2.4 epoxide equivalents and 7.14 equivalents of bromine.

Br-CH Br-CH Example 6 In the course of 2 hours at to C., 71 parts (1mol) of chlorine are introduced into a solution of 242.5 parts (1 mol)of a-cmonochlorohydrin ether of S-hydroxy-dihydro-dicyclopentadiene (8hydroxy-tricyclo[5.2.1;0 ]decene-4) in 100 parts by volume of benzene.The whole is then dilute with 100 parts by volume of benzene, and 165parts (1.5 mols) of sodium hydroxide solution of 36.4% strength areadded dropwise, while allowing the temperature to rise to about 50 C.The mixture is stirred for 30 minutes without cooling or heating, thencooled, and the product is worked up as described in Example 8 bytreating it once more with 1 mol of sodium hydroxide solution of 50%strength for 40 minutes at 50 C. Finally, there are obtained 230.5 partsof the dichlorinated dihydro-dicycllo-pentadiene glycidyl ether of theformula as a brown, viscous liquid containing 1.77 epoxide groups perkg. and 24.5% of chlorine.

Example 7 290 parts (0.96 mol) of 3:4-dibromocyclohexane-1:ldimethanol(melting at 137138 C.) are mixed with 300 parts of benzene and 2 partsof tin tetrachloride are added. The mixture is heated to 70 C., and inthe course of 20 minutes 187 parts (2.02 mols) of epichlorohydrin arestirred in dropwise, while cooling to maintain the temperature at 70 to75 C. The mixture is then stirred for 30 minutes at the sametemperature, cooled to 25 C., and 324 parts (2.4 mols) of sodiumhydroxide solution of 29.6% strength are added. During this addition thetemperature rises only slightly and is maintained by heating for 1 hourat 70 C. The mixture is allowed to cool slightly, 100 parts of Water areadded to dissolve the salt, and the benzene layer is separated andstirred at 70 C. for 1 hour with 70 parts (0.96 mol) of sodium hydroxidesolution of 50% strength. The whole is then allowed to cool slightly, 90parts of Water are added, and the henzene layer is separated, dried overcalcium chloride and evaporated, to yield 391 parts of an almostcolorless liquid having the same properties as the diglycidyl etherobtained in Example 2.

Example 8 A solution of 20 parts of the diglycidyl ether dibrominated asdescribed in Example 2 in 8 parts of a mixture of 3 parts of butanol, 1part of ethyleneglycol monoethyl ether and 4 parts of xylene is mixedwith parts Example 9 An intimate mixture is prepared from 100 parts ofthe diglycidyl ether obtained as described in Example 2,

12 parts of triethylene tetramine and 4 parts of his-(l:2:4-dimethylaminomethyl)-phenol. Oak panels measuring 22 9 1 cm. arebrushed with this mixture, a glass fiber fabric (Asl-3l4 of Messrs.Fibres de Verre, Lausanne) is interposed, and after gelling another coatis applied to the sandwich. A smooth, well adherent protective coatresults. A flammability test carried out along the lines laid down inDIN 53382 reveals that the material is still inflammable but isimmediately extinguished when the flame is removed from it.

Example 10 An intimate mixture is prepared from parts of the diglycidylether manufactured according to Example 2, 15 parts oftriethylenetetramine and 2.5 parts of a melamine-formaldehyde condensateether-ified with butanol is applied in a thickness of about 250,11. toaluminum sheet. At room temperature this coating undergoes curingovernight to form a hard, and yet flexible coat of high lustre.

Example 11 A mixture is prepared from 65 parts of a diglycidyl ether,which is liquid at room temperature, ofbis-(4-hydroxyphenyhdimethylmethane (containing 5.2 epoxide equivalentsper kg.) and 35 parts of the dibrominated diglycidy-l ether, prepared asdescribed in Example 2, containing 4.1 epoxide epoxide equivalents perkg. The resin mixture is intimately mixed with 11.75 parts oftriethylenetetramine as curing agent. A 12-ply glass fiber laminate (A)is manually covered with this mixture, the glass fiber fabric being aVertrotex fabric Type 354 AFI of Messrs. Fibres de Verre, Lausanne. Thislaminate is then cured for 24 hours at 40 C.

For comparison another laminate (B) is prepared under identicalconditions, but in this case the dibrominated diglycidyl ether ofExample 2 is omitted.

As shown by the values in the following table, laminate A isself-extinguishing and more water-repellent than laminate B:

Bending Water abstrength sorption, Shape re- Bending after 10 after 10tention on Lamistrength days residays resiheating Inflammanate in kg./dence in dance in acedg. to bility mm. water at water at Martens 20 C.in 20 C. in (DIN), kg./m1n. percent C.

A 19.0 17. 0 1. 15 59 Self-extinguishing. B 21. 3 16. 9 1. 42 62 Noextinction after removal of flame.

wherein the two radicals Hal each are selected from the group consistingof chlorine atom and bromine atom, R is a member selected from the groupconsisting of hydrogen atom and the methyl group and R and R areselected from the group consisting of hydrogen atom and together 7 R andR form the methylene group, compounds of the formula wherein the tworadicals Hal each are selected from the group consisting of chlorineatom and bromine atom, R is a member selected from the group consistingof hydrogen atom and the methyl group, and R and R are hydrogen, andcompounds of the formula l C-R1 O 3. The compound of the formula CH; O

4. The compound of the formula Br-OH Br-CH 5. The compound of theformula References Cited in the file of this patent UNITED STATESPATENTS Clemens et al June 29, 1954 Parret et a1 July 11, 1961 OTHERREFERENCES Australian Abstract, 58,311/60, Sept. 15, 1960.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3, 151,129 September 29 -1964 Ernst Leumann et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patentshould read ascorrected below.

Column 6, lines 56 to 63, for the upper left-hand portion of the formulareading Y read Signed and sealed this 23rd day of February 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo., 3, 151 129 September 29--,- 1964 Ernst Leumann et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 6, lines 56 to 63, for the upper left-hand portion of the formulareading R 3 I R 3 read Signed and sealed this 23rd day of February 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Altesting Officer Commissioner ofPatents

1. GLYCIDYL ETHERS SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OFFORMULA